NO141056B - PAPER ADHESIVE AND METHOD OF PREPARATION - Google Patents
PAPER ADHESIVE AND METHOD OF PREPARATION Download PDFInfo
- Publication number
- NO141056B NO141056B NO744281A NO744281A NO141056B NO 141056 B NO141056 B NO 141056B NO 744281 A NO744281 A NO 744281A NO 744281 A NO744281 A NO 744281A NO 141056 B NO141056 B NO 141056B
- Authority
- NO
- Norway
- Prior art keywords
- mol
- paper
- diisobutylene
- maleic anhydride
- parts
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims description 27
- 230000001070 adhesive effect Effects 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 2
- 238000004513 sizing Methods 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- -1 aliphatic amines Chemical class 0.000 claims description 8
- 150000008064 anhydrides Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000004026 adhesive bonding Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- AVWWPFWBTLONRB-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.CC(C)=C.O=C1OC(=O)C=C1 AVWWPFWBTLONRB-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/04—Anhydrides, e.g. cyclic anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Papirlimingsmiddel og fremgangsmåte til fremstilling derav.Paper sizing agent and method of making the same.
Description
Oppfinnelsen vedrører anioniske limingsmidler for papir eller papirlignende materialer av halvestere av diisobutylen-maleinsyreanhydrid/kopolymerisater i form av deres alkali-, amin- eller ammoniumsalter. The invention relates to anionic sizing agents for paper or paper-like materials of half-esters of diisobutylene-maleic anhydride/copolymers in the form of their alkali, amine or ammonium salts.
Det er kjent å fremstille kopolymerisater av diisobutylen og maleinsyreanhydrid ved radikalisk kopolymerisasjon (US-patent nr. 2.378.629). It is known to prepare copolymers of diisobutylene and maleic anhydride by radical copolymerization (US patent no. 2,378,629).
Det er videre kjent å fremstille terpolymerisater av 2-3 mol maleinsyreanhydrid, 3-2 mol- diisobutylen og 0,3-5 vekt%, referert til summen av maleinsyreanhydrid og diisobutylen, av divinylbenzen og å anvende alkali- resp. ammoniumsalter av disse It is further known to prepare terpolymers of 2-3 mol of maleic anhydride, 3-2 mol of diisobutylene and 0.3-5% by weight, referred to the sum of maleic anhydride and diisobutylene, of divinylbenzene and to use alkali resp. ammonium salts of these
terpolymerisater for overflateliming av papir (US-patent nr. 2.725.367). I dette patent fremheves og påvises med tall at alkali- resp. ammoniumsaltene -av terpolymerisatene har en vesentlig bedre limingsvirkning for papir enn tilsvarende salter av kopolymerisater av maleinsyreanhydrid og diisobutylen. terpolymers for surface sizing of paper (US patent no. 2,725,367). In this patent, it is emphasized and demonstrated with numbers that alkali- or the ammonium salts of the terpolymers have a significantly better gluing effect for paper than corresponding salts of copolymers of maleic anhydride and diisobutylene.
Oppfinnelsens oppgave var å modifisere de kjente limingsmidler på basis av maleinsyreanhydrid/diisobutylenkopoly-merisater således at det oppnås bedre limingsvirkninger enn med de kjente midler, og nemlig i det vesentlige uavhengig av pH-verdien. The task of the invention was to modify the known gluing agents based on maleic anhydride/diisobutylene copolymers so that better gluing effects are achieved than with the known agents, and namely essentially independent of the pH value.
Oppgave ble løst ved at i diisobutylen-maleinsyreanhydrid-kopolymerisater værende anhydridgrupper delvis eller fullstendig ble overført til halvestere og deretter de resterende anhydrid- resp. karboksylgruppene delvis eller fullstendig omdannes til alkali-, amin- og ammoniumsalter og anvendes som limingsmiddel. The task was solved by the fact that anhydride groups present in diisobutylene-maleic anhydride copolymers were partially or completely transferred to half-esters and then the remaining anhydride-resp. the carboxyl groups are partially or completely converted into alkali, amine and ammonium salts and are used as adhesives.
Oppfinnelsens gjenstand er således anioniske limingsmidler inneholdende vandige eller vandig-alkoholiske alkali-, alifatiske amin- eller ammoniumsaltoppløsninger av i det vesentlige ekvimolekylær oppbyggede kopolymerisater av maleinsyreanhydrid og diisobutylen, idet limingsmidlene er karakterisert ved at de dannede anhydridgrupper er forestret med lineære eller forgrenede alifatiske monoalkoholer med 1-20 C-atomer eller med cykloalifatiske monoalkoholer med 5-6 C-atomer til 10-100 mol% til tilsvarende halvestere. The object of the invention is thus anionic adhesives containing aqueous or aqueous-alcoholic alkali, aliphatic amine or ammonium salt solutions of essentially equimolecularly structured copolymers of maleic anhydride and diisobutylene, the adhesives being characterized in that the anhydride groups formed are esterified with linear or branched aliphatic monoalcohols with 1-20 C atoms or with cycloaliphatic monoalcohols with 5-6 C atoms to 10-100 mol% to corresponding half-esters.
For fremstilling av limingsmiddel ifølge oppfinnelsen anvender man på radikalsk måte fremstilte kopolymerisater av 0,9-1,1 mol maliensyreanhydrid og 1,1-0,9 mol diisobutylen. Ved siden av sin rene form kan diisobutylen også anvendes i form av dens tekniske blandinger. Til utløsing av denne kopolymerisasjon kan det anvendes radikaldannende stoffer, som f.eks. peroksyd, hydroperoksyder, perestere, azoforbindelser, samt redokskataly-satorsystemer. For the production of the adhesive according to the invention, radical copolymers of 0.9-1.1 mol of maleic anhydride and 1.1-0.9 mol of diisobutylene are used. In addition to its pure form, diisobutylene can also be used in the form of its technical mixtures. To trigger this copolymerisation, radical-forming substances can be used, such as e.g. peroxide, hydroperoxides, peresters, azo compounds, as well as redox catalyst systems.
Polymerisasjonen kan gjennomføres uten trykk i stoff eller fortrinnsvis i oppløsning. Foregår den i oppløsning, så er det foretrukket slike oppløsningsmidler, hvori det oppløser seg såvel det monomere som også de kopolymere, f.eks. aromater som benzen, toluen, halogenerte aromater som klorbenzen, klortoluen, lavere ketoner som aceton, etylmetylketon, estere av lavere fettsyrer som eddiksyreetylester, klorerte alifatiske hydrokarboner som kloroform, karbontetraklorid, etere som tetrahydrofuran, sterkt polare oppløsningsmidler som dimetylformamid eller dimetylsulfoksyd. Polymerisasjonstemperaturen ligger mellom 20 og 150°C, fortrinnsvis imidlertid mellom 30 og 120°C. The polymerization can be carried out without pressure in substance or preferably in solution. If it takes place in solution, such solvents are preferred, in which the monomer as well as the copolymers dissolve, e.g. aromatics such as benzene, toluene, halogenated aromatics such as chlorobenzene, chlorotoluene, lower ketones such as acetone, ethyl methyl ketone, esters of lower fatty acids such as acetic acid ethyl ester, chlorinated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, ethers such as tetrahydrofuran, strongly polar solvents such as dimethylformamide or dimethylsulfoxide. The polymerization temperature is between 20 and 150°C, preferably between 30 and 120°C.
De dannede kopolymerisater kan omdannes til halvestere ved omsetning med en 0,1-5,0 mol, fortrinnsvis 0,2-1 mol, referert til 1 mol maleinsyreanhydridgrupper i kopolymerisåtet av alifatiske lineære eller forgrenede C2._<C>20' f°rtr:i-nnsv:i-s ci_C8 monoalkoh°ler' som metanol, etanol, propanol, isopropanol, butanol, amylalkohol, isoamylalkohol, hexanol, 2-etylhexanol, dodekanol, oktadekanol, fortrinnsvis isopropanol eller etanol, eller cykloalifatiske C^-C^-monoalkoholer, fortrinnsvis cyklohexanol til 10 til 100 mol%, spesielt 15 til 50 mol%, av det refererte anhydrid. Herved foregår halvesterdannelsen enten i stoff eller i et oppløsningsmiddel, hvori såvel den kopolymere som halvesteren er oppløselige, f.eks. The copolymers formed can be converted into half-esters by reaction with a 0.1-5.0 mol, preferably 0.2-1 mol, referred to 1 mol of maleic anhydride groups in the copolymer seed of aliphatic linear or branched C2._<C>20' f° rtr:i-nnsv:i-s ci_C8 monoalcohols' such as methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, isoamyl alcohol, hexanol, 2-ethylhexanol, dodecanol, octadecanol, preferably isopropanol or ethanol, or cycloaliphatic C^-C^- monoalcohols, preferably cyclohexanol to 10 to 100 mol%, especially 15 to 50 mol%, of the referred anhydride. Hereby, the half-ester formation takes place either in substance or in a solvent, in which both the copolymer and the half-ester are soluble, e.g.
i ovennevnte alkoholer, aromatiske hydrokarboner som toluen, halogenerte aromater som klorbenzen, klortoluen, lavere ketoner som aceton, etylmetylketon, estere av lavere fettsyrer som etylacetat, klorerte alifatiske hydrokarboner som karbontetraklorid, etere in the above alcohols, aromatic hydrocarbons such as toluene, halogenated aromatics such as chlorobenzene, chlorotoluene, lower ketones such as acetone, ethyl methyl ketone, esters of lower fatty acids such as ethyl acetate, chlorinated aliphatic hydrocarbons such as carbon tetrachloride, ethers
som tetrahydrofuran, sterkt polare oppløsningsmidler som dimetylformamid, dimetylsulfoksyd, og lignende ved temperaturer mellom 20 og 120°C, fortrinnsvis mellom 20 og 90°C. De i limingsmidlet ifølge oppfinnelsen inneholdte kopolymerisater er vanligvis opp-bygget alternerende og ekvimolekylært og har polymerisasjonsgrader mellom 20 og 800, fortrinnsvis mellom 80 og 120. such as tetrahydrofuran, strongly polar solvents such as dimethylformamide, dimethylsulfoxide, and the like at temperatures between 20 and 120°C, preferably between 20 and 90°C. The copolymers contained in the adhesive according to the invention are usually structured alternately and equimolecularly and have degrees of polymerization between 20 and 800, preferably between 80 and 120.
Selvsagt er det også mulig å polymerisere diisobutylen direkte med de ønskede maleinsyrehalvestere under de samme be-tingelser som ved diisobutylen-maleinsyreanhydridkopolymerisa-sjonen til de tilsvarende kopolymerisater. Of course, it is also possible to polymerize diisobutylene directly with the desired maleic acid half-esters under the same conditions as in the diisobutylene-maleic anhydride copolymerization to the corresponding copolymers.
Overføringen av omsetningsproduktene av maleinsyreanhydrid-diisobutylenkopolymerisater og monoalkoholer i deres alkali- eller ammoniumsalter kan foregå ved hjelp av hydroksydene av alkalimetallene eller ved primære, sekundære eller tertiære alifatiske aminer, som f.eks. metylamin, dimetylamin, etanolamin, trietylamin, dietanolamin eller trietanolamin, imidlertid er anvendelsen av vandig ammoniakk foretrukket. The transfer of the reaction products of maleic anhydride-diisobutylene copolymers and monoalcohols in their alkali or ammonium salts can take place by means of the hydroxides of the alkali metals or by primary, secondary or tertiary aliphatic amines, such as e.g. methylamine, dimethylamine, ethanolamine, triethylamine, diethanolamine or triethanolamine, however, the use of aqueous ammonia is preferred.
Mengden av de for saltdannelse anvendte alkali-, alifatiske amin- eller ammoniakkmengder er ikke kritiske, og et overskudd påvirker på ingen måte limingsvirkningen av produktene ifølge oppfinnelsen. Av fysikalske grunner er det imidlertid referert til de frie karboksylgrupper resp. anhydridgrupper, foretrukket støkiometriske eller også mindre enn støkiometriske mengder av alkali, alifatiske aminer eller ammoniakk. Anvendes støkiometriske underskytende mengder, så bør minst 50 mol% av de i kopolymerisatet inneholdte karboksylgrupper, nøytraliseres med alkali, alifatiske aminer eller ammoniakk. For å oppnå vann-oppløselige produkter bør 80-100 mol% av karboksylgruppen resp. anhydridgruppene nøytraliseres. The amount of alkali, aliphatic amine or ammonia used for salt formation is not critical, and an excess in no way affects the gluing effect of the products according to the invention. For physical reasons, however, reference is made to the free carboxyl groups or anhydride groups, preferably stoichiometric or also less than stoichiometric amounts of alkali, aliphatic amines or ammonia. If below-stoichiometric quantities are used, then at least 50 mol% of the carboxyl groups contained in the copolymer should be neutralized with alkali, aliphatic amines or ammonia. To obtain water-soluble products, 80-100 mol% of the carboxyl group or the anhydride groups are neutralized.
Overføringen av kopolymerisatet i deres alkali-, amin- eller ammoniumsalter kan enten foregå ved oppløsningen av de utfelte pulverformede halvesterprodukter i vandige oppløs-ninger av alkali-, alifatiske amin- eller ammoniumforbindelser, eller ved tilsetning av de vandige alkali- eller ammoniumforbindelser til oppløsningene av halvesterpolymerisatene. I sist-nevnte tilfelle kan den derved dannede oppløsning eller emulsjon anvendes som sådan eller det kan også fjernes oppløsningsmidlet eller oppløsningsmidlene ved destillering eventuelt i vakuum, idet det alltid oppstår en luktfri, omtrent farveløs vandig opp-løsning. The transfer of the copolymer in their alkali, amine or ammonium salts can either take place by dissolving the precipitated powdery half-ester products in aqueous solutions of alkali, aliphatic amine or ammonium compounds, or by adding the aqueous alkali or ammonium compounds to the solutions of the half-ester polymers. In the latter case, the resulting solution or emulsion can be used as such or the solvent or solvents can also be removed by distillation, possibly in a vacuum, since an odorless, approximately colorless aqueous solution is always produced.
Limingsmidlet ifølge oppfinnelsen har et bredt anvendelsesspektrura for liming av papir. De kan anvendes på The gluing agent according to the invention has a broad application spectrum for gluing paper. They can be applied to
ulimt, vanlig forlimt og i kombinasjon med andre limingsmidler, fortrinnsvis i overflaten. En ytterligere fordel med disse limingsmidler er at de også virker limende på papir med lite eller overhode,intet innhold av flerverdig metallioner, f.eks. aluminiumioner, og at de ikke påvirker virkningen av hvittonere. unglued, normally pre-glued and in combination with other adhesives, preferably in the surface. A further advantage of these adhesives is that they also have an adhesive effect on paper with little or no content of polyvalent metal ions, e.g. aluminum ions, and that they do not affect the effect of white toners.
De kan komme til anvendelse sammen med sure, nøytrale eller They can be used together with acidic, neutral or
også basiske fyllstoffer som kritt, kaolin, kina clay eller andre og med tilsetningsstoffer som karboksymetylcellulose eller spesielt stivelse. also basic fillers such as chalk, kaolin, china clay or others and with additives such as carboxymethyl cellulose or especially starch.
Som ekstra overraskende effekter viser de nye limingsmidler ingen følsomhet overfor svingninger av pH-området i lime-badet. Således er ved pH-verdier mellom 4 og 11, fortrinnsvis mellom 5 og 10, limingsvirkningen alltid god, såvel ved anvendelse av ulimt som også på konvensjonelt forlimt papir. As additional surprising effects, the new gluing agents show no sensitivity to fluctuations in the pH range in the gluing bath. Thus, at pH values between 4 and 11, preferably between 5 and 10, the gluing effect is always good, both when using unglued and also on conventional pre-glued paper.
De nye limingsmidler bringes i handel i form av deres vandige eller vandig-alkoholiske oppløsninger, fortrinnsvis i form av vandige oppløsninger av deres ammoniumsalter eller alkali-salter med et faststoffinnhold fra 5 til 75 vekt%. Imidlertid anvendes de ved limingsprosessen selv ofte i sterkt fortynnet form med faststoffinnhold fra 0,005 til 10 vekt%. The new adhesives are marketed in the form of their aqueous or aqueous-alcoholic solutions, preferably in the form of aqueous solutions of their ammonium salts or alkali salts with a solids content of from 5 to 75% by weight. However, in the gluing process itself, they are often used in highly diluted form with a solids content of from 0.005 to 10% by weight.
Påføringen kan foregå ved tilblandingen til papir-raassen med etterfølgende impregnering eller sprøyting av bladet og ellers vanlig fremgangsmåter. The application can take place by mixing it into the paper pulp with subsequent impregnation or spraying of the leaf and other usual methods.
I det følgende skal det eksempelvis forklares fremstilling og virkningsmåte av de nye limingsmidler. De angitte deler og prosentinnhold refererer seg til vekt, hvis intet annet er bemerket. In the following, for example, the production and mode of action of the new adhesives will be explained. The parts and percentages given refer to weight, if nothing else is noted.
L imingsmiddel A Adhesive A
I en 40 liters stålautoklav oppvarmer man under lett nitrogenovertrykk 2940 deler maleinsyreanhydrid, 4500 deler diisobutylen og 4080 deler tørr toluen til 75°C. I denne oppløs-ning inndoseres.iløpet av 3 timer 63 deler azodiisobutyronitril som radikalinitiator i 1080 deler tørr toluen. Etter 6 timers reaksjonstid økes temperaturen til 85°C og det tilsettes dessuten 31,5 deler azodiisobutyronitril i 540 deler toluen. Etter ytterligere 6 timer økes temperaturen til 95°C og bibeholdes så lenge inntil det er inntrådt en kvantitativ polymerisering av de monomere. Deretter senkes temperaturen til 80°C og det tilsettes en oppløsning av 900 deler isopropanol i 750 deler toluen og omrøres ennå 2 timer ved denne temperatur. Til den dannede klare høyviskøse polymeroppløsning tilsettes 24.500 deler elektrolytvann og 4300 deler ca. 25%-ig vandig ammoniakkoppløsning. Deretter destillerer man under omrøring og anlegg av et svakt vakuum ved 80°C toluenet så lenge azeotropisk over en destilla-sjonsbro med tilbakeløp inntil det er kommet en klar, svak gulfarvet oppløsning ved tilbakeløpet. Denne oppløsning som har et faststoffinnhold på 20 vekt% kan anvendes direkte respektivt etter tilsvarende fortynning med vann som limingsmiddel. In a 40 liter steel autoclave, 2940 parts of maleic anhydride, 4500 parts of diisobutylene and 4080 parts of dry toluene are heated to 75°C under slight nitrogen overpressure. In this solution, 63 parts of azodiisobutyronitrile as a radical initiator are dosed in 1080 parts of dry toluene over the course of 3 hours. After a reaction time of 6 hours, the temperature is increased to 85°C and 31.5 parts of azodiisobutyronitrile in 540 parts of toluene are also added. After a further 6 hours, the temperature is increased to 95°C and maintained until a quantitative polymerization of the monomers has occurred. The temperature is then lowered to 80°C and a solution of 900 parts isopropanol in 750 parts toluene is added and stirred for a further 2 hours at this temperature. To the clear highly viscous polymer solution formed, 24,500 parts of electrolyte water and 4,300 parts approx. 25% aqueous ammonia solution. The toluene is then distilled azeotropically over a distillation bridge with reflux until a clear, faintly yellow solution is obtained at the reflux, while stirring and applying a weak vacuum at 80°C. This solution, which has a solids content of 20% by weight, can be used directly or after corresponding dilution with water as adhesive.
Limingsmiddel B Adhesive B
21,0 deler av en 1:1 kopolymer av maleinsyreanhydrid og diisobutylen som ved limingsmiddel A, imidlertid isolert som pulver, oppløses i 140 deler tetrahydrofuran. Etter at det til denne oppløsning ble satt to dråper konsentrert svovelsyre, drypper man ved værelsetemperatur inn 1,6 deler metanol i 25 deler tetrahydrofuran og oppvarmer ennå i to timer under tilbakeløp. Den dannede polymeroppløsning (halvester) inndryppes under om-røring i et overskudd av eter og det derved utfelte hvite pulver tørkes 24 timer i vakuum ved 60°C. Ved oppløsning av 18,0 vektdeler av dette pulver i 82 vektdeler ca. 3%-ig vandig NH^-opp-løsning fåes en klar, farveløs oppløsning med ca. 20 vekt% fast-stoff. Denne oppløsning kan anvendes direkte eller etter.tilsvarende fortynning som limingsmiddel. 21.0 parts of a 1:1 copolymer of maleic anhydride and diisobutylene as in adhesive agent A, however isolated as a powder, are dissolved in 140 parts of tetrahydrofuran. After two drops of concentrated sulfuric acid have been added to this solution, 1.6 parts of methanol in 25 parts of tetrahydrofuran are dripped in at room temperature and heated for a further two hours under reflux. The formed polymer solution (half ester) is added dropwise with stirring into an excess of ether and the resulting white powder is dried for 24 hours in a vacuum at 60°C. When dissolving 18.0 parts by weight of this powder in 82 parts by weight approx. 3% aqueous NH 3 solution gives a clear, colorless solution with approx. 20% by weight solids. This solution can be used directly or after similar dilution as a glue agent.
Limingsmiddel C Adhesive C
Fremstilling av analogt limingsmiddel B, det anvendes imidlertid i stedet for metanol 4,4 deler isoamylalkohol. Preparation of analogous adhesive B, however, 4.4 parts of isoamyl alcohol are used instead of methanol.
Limingsmiddel D Adhesive D
Fremstilling analogt limingsmiddel B og C, det anvendes imidlertid i stedet for metanol resp. isoamylalkohol 3,0 deler isopropanol. Production analogous to adhesives B and C, however, it is used instead of methanol or isoamyl alcohol 3.0 parts isopropanol.
Limingsmiddel E Adhesive E
I en 1 liters trehalset kolbe med rører, indre termometer, dryppetrakt, tilbakeløpskjøler, N2~inn- og utløp polymeriserer man en blanding av 98 deler maleinsyreanhydrid, In a 1 liter three-necked flask with stirrer, internal thermometer, dropping funnel, reflux condenser, N2 ~ inlet and outlet, a mixture of 98 parts maleic anhydride,
150 deler diisobutylen og 136 deler tørr toluen ved tildrypping av 2,10 deler benzoylperoksyd i 36 deler toluen ved 80°C. Etter 24 timer polymerisasjonstid drypper man til denne polymeroppløs-ning en oppløsning av 30 deler isopropanol i 25 deler toluen og oppvarmer ennå 2 timer under tilbakeløp. Deretter tilsettes 660 deler elektrolytvann og 116 deler 25%-ig ammoniakk. Fra den dannede emulsjon fjernes nå under anlegg av et svakt vakuum og ved en temperatur mellom 80 og 90°C resterende oppløsningsmid-del. Det oppstår endelig en klar, svak gulfarvet oppløsning med et faststoffinnhold på 21,8 vekt% som anvendes direkte eller etter tilsvarende fortynning som limingsmiddel. 150 parts of diisobutylene and 136 parts of dry toluene by adding dropwise 2.10 parts of benzoyl peroxide in 36 parts of toluene at 80°C. After 24 hours of polymerization time, a solution of 30 parts of isopropanol in 25 parts of toluene is dripped into this polymer solution and heated for a further 2 hours under reflux. 660 parts of electrolyte water and 116 parts of 25% ammonia are then added. The remaining solvent is now removed from the emulsion formed under the application of a weak vacuum and at a temperature between 80 and 90°C. Finally, a clear, faintly yellow solution with a solids content of 21.8% by weight is produced, which is used directly or after a corresponding dilution as a bonding agent.
Limingsmiddel F Adhesive F
Fremstillingen foregår analogt limingsmiddel B, imidlertid anvendes i stedet for metanol 5,0 deler cyklohexanol. The production takes place analogously to adhesive B, however, instead of methanol, 5.0 parts of cyclohexanol are used.
Limingsmiddel G Adhesive G
Fremstillingen foregår analogt limingsmiddel B, imidlertid anvendes i stedet for metanol 13,5 deler stearylalkohol. The production takes place analogously to adhesive B, however instead of methanol 13.5 parts of stearyl alcohol are used.
I det følgende er det eksempelvis omtalt anvendelsen av limingsmidlene A-G. In the following, for example, the use of the adhesives A-G is discussed.
Det anvendte ulimte papir er fremstilt under tilsetning av ca. 1,5% aluminiumsulfat, referert til tørt råstoff, The unglued paper used is produced with the addition of approx. 1.5% aluminum sulphate, referred to dry raw material,
av bleket sulfittcellulose og har en vekt pa ca. 80 g/m 2. of bleached sulphite cellulose and has a weight of approx. 80 g/m2.
Det anvendte forlimte papir er fremstilt av bleket sulfitcellulose under tilsetning av ca. 0,3% vanlig harpikslim (Abienat-basis) og ca. 2% aluminiumsulfat (referert til tørr cellulose) og har likeledes en kvadratmetervekt på ca. 80 g. The pre-glued paper used is made from bleached sulphite cellulose with the addition of approx. 0.3% regular resin glue (Abienat base) and approx. 2% aluminum sulphate (referred to dry cellulose) and likewise has a square meter weight of approx. 80 g.
Som limingsbad for overflatelimingen ble det anvendt en oppløsning av 5 vekt?, stivelse ("Perf ectamyl" A 4692 fra firma AVEBE) og 0,2 til 0,4% av limingsmidlet som skal under-søkes (beregnet som 100%-ig virksomt stoff) i 94,8-94,6 vekt% vann. A solution of 5% starch ("Perf ectamyl" A 4692 from the company AVEBE) and 0.2 to 0.4% of the gluing agent to be examined (calculated as 100% effective) was used as the gluing bath for the surface gluing substance) in 94.8-94.6 wt% water.
For limingen ble det anvendt en laboratorielimpresse fra firma Werner Mathis, Ziirich, Sveits, type HF. Limingsbadet hadde i limpressen en temperatur på ca. 20°C og en væskestand på ca. 3 cm høyde. Papiret ble trukket gjennom med en hastighet på 4 m/ min. For the gluing, a laboratory glue press from the company Werner Mathis, Ziirich, Switzerland, type HF, was used. The gluing bath in the glue press had a temperature of approx. 20°C and a liquid level of approx. 3 cm height. The paper was pulled through at a speed of 4 m/min.
Tørking av de overflatelimte papir foregikk på en tørkesylinder iløpet av ett minutt ved ca. 100°C. Før limings-prøven ble papirene klimatisert i 2 timer ved værelsetemperatur. Avsnitt av papirene forveies deretter, dyppes ett minutt i vann av 20°C, avpresses mellom filterpapir ved hjelp av en 10 kg rullevekt en gang og igjen veies. Fra vektdifferansen ble det beregnet verdien av det beggesidige vannopptak i g/m . Jo mindre vannopptaket er, desto bedre er virkningen av det undersøkte limingsmiddel. En god liming foreligger når det oppnås et vannopptak pa ca. 4 0 g/m 2 og lavere. Drying of the surface-glued paper took place on a drying cylinder within one minute at approx. 100°C. Before the gluing test, the papers were conditioned for 2 hours at room temperature. Sections of the papers are then pre-weighed, dipped in water at 20°C for one minute, pressed between filter papers using a 10 kg roll scale once and weighed again. From the weight difference, the value of the water absorption on both sides in g/m was calculated. The smaller the water absorption, the better the effect of the tested adhesive. Good bonding is achieved when a water absorption of approx. 40 g/m 2 and lower.
De i tabellene angitte %-angivelser refererer seg til mengden av det i badet inneholdende limingsmiddel beregnes som 100%-ig virksomt stoff. The percentages given in the tables refer to the amount of adhesive contained in the bath, calculated as 100% active substance.
Eksempel 1- 5 Example 1-5
Følgende tabell 1 viser at det med de omtalte limingsmidler på ulimt, aluminiumionholdig papir er å oppnå gode limingseffekter: The following table 1 shows that good gluing effects can be achieved with the gluing agents mentioned on unglued, aluminum ion-containing paper:
Eksempel 6- 10 Example 6-10
Tabell 2 viser vannopptak av forlimt papir som ble overflatelimt i en limpresse: Table 2 shows the water absorption of pre-glued paper that was surface-glued in a glue press:
Sammenligningseksempel 1 Comparative example 1
Her ble det påvist en i forhold til produktet fremstilt ifølge US-patent nr. 2.725.367 forbedrede limingsvirkning av limingsmidlet ifølge oppfinnelsen ved hjelp av limingsmiddel D. Here, compared to the product manufactured according to US patent no. 2,725,367, an improved gluing effect of the gluing agent according to the invention using gluing agent D was demonstrated.
Sammenligningseksempel 2 Comparative example 2
Det vises her at limingsmidlene ifølge oppfinnelsen i forhold til et limingsmiddel fra teknikkens stand (ammonium-salt av et 1:1 kopolymerisat av styren og maleinsyreisopropyl-halvester), har en betraktelig bedre liming på ulimt og forlimt papir. It is shown here that the gluing agents according to the invention compared to a gluing agent from the state of the art (ammonium salt of a 1:1 copolymer of styrene and maleic acid isopropyl half-ester), have a considerably better gluing on unglued and pre-glued paper.
Eksempel 11 Example 11
Med limingsmiddel D som eksempel ytterliggjøres ufølsomheten av limingsmidlet ifølge oppfinnelsen overfor varia-sjoner av pH-verdier såvel ved ulimt som ved forlimt papir. With sizing agent D as an example, the insensitivity of the sizing agent according to the invention to variations in pH values both for unglued and pre-glued paper is further enhanced.
Tabell 5: Innvirkning av pH på overflatemiling av ulimt og forlimt papir. Table 5: Effect of pH on surface miling of unglued and pre-glued paper.
Tilsetning av limingsmidlet (100%-ig) til badet 0,08%. Vannopptak av det ulimte råpapir: 9 4 g/m 2. Vannopptak av forlimt råpapir: 59 g/m 2. Addition of the gluing agent (100%-ig) to the bath 0.08%. Water absorption of the unglued raw paper: 9 4 g/m 2. Water absorption of pre-glued raw paper: 59 g/m 2.
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DE2361544A DE2361544C3 (en) | 1973-12-11 | 1973-12-11 | Paper sizing agents |
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NO744281L NO744281L (en) | 1975-07-07 |
NO141056B true NO141056B (en) | 1979-09-24 |
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JP (1) | JPS5926719B2 (en) |
AT (1) | AT340767B (en) |
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CA (1) | CA1030287A (en) |
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DE2701760C3 (en) * | 1977-01-18 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Process for the production of paper sizing agents |
JPS5427003A (en) * | 1977-08-03 | 1979-03-01 | Nippon Oil Co Ltd | Sizing agent for paper making |
DE2840650A1 (en) * | 1978-09-19 | 1980-03-27 | Bayer Ag | Low froth paper surface size based on copolymer of maleic anhydride! - and di:isobutylene! in form of soluble salt of half amide |
NO792863L (en) * | 1978-09-19 | 1980-03-20 | Bayer Ag | SCRAPFUL SURFACE PAPER |
JPS5567094A (en) * | 1978-11-13 | 1980-05-20 | Hitachi Chemical Co Ltd | Production of paper with good sizing degree |
JPS5584491A (en) * | 1978-12-15 | 1980-06-25 | Kurita Water Ind Ltd | Pitch attachment preventing agent for paper making |
JPS58214598A (en) * | 1982-06-07 | 1983-12-13 | 三菱石油株式会社 | Papermaking size agent |
BE895801A (en) * | 1983-02-04 | 1983-05-30 | Felix Schoeller Jr G M B H | PHOTOGRAPHIC PAPER SUPPORT |
DE3319014A1 (en) * | 1983-05-26 | 1984-11-29 | Bayer Ag, 5090 Leverkusen | COPOLYMERS AND THEIR USE AS SIZE |
DE3429961A1 (en) * | 1984-08-16 | 1986-02-27 | Bayer Ag, 5090 Leverkusen | SURFACE SIZING AGENT FOR PAPER |
JPS61119798A (en) * | 1984-11-14 | 1986-06-06 | 株式会社 千代田化学研究所 | Size agent |
US4629655A (en) * | 1985-06-27 | 1986-12-16 | A. E. Staley Manufacturing Company | Size composition |
EP0224976B1 (en) * | 1985-11-29 | 1989-10-18 | Kabushiki Kaisha Chiyoda Kagaku Kenkyusho | Method of sizing paper |
DE3609981A1 (en) * | 1986-03-25 | 1987-10-01 | Bayer Ag | SURFACE SIZING AGENT FOR PAPER |
JPH0411931Y2 (en) * | 1986-12-03 | 1992-03-24 | ||
US5453476A (en) * | 1993-08-23 | 1995-09-26 | Rohm And Haas Company | High solids copolymerization via in-situ isomerization |
EP0701019A1 (en) * | 1994-06-21 | 1996-03-13 | Giulini Chemie GmbH | Amphoteric sizing agent for papier acid production process thereof |
DE69609947T2 (en) * | 1995-01-27 | 2001-04-12 | Tyco Electronics Corp., Menlo Park | GELS MADE OF POLYMERS CONTAINING ANHYDRIDE |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2378629A (en) * | 1941-09-10 | 1945-06-19 | Du Pont | Copolymers of maleic anhydride |
US2725367A (en) * | 1953-01-29 | 1955-11-29 | Rohm & Haas | Salts of terpolymers of maleic anhydride, diisobutylene and divinylbenzene |
US2930775A (en) * | 1958-10-14 | 1960-03-29 | Rohm & Haas | Pigment pastes containing water-soluble diisobutylene-maleic anhydride copolymer salts |
US3322713A (en) * | 1964-06-04 | 1967-05-30 | Monsanto Co | Dispersion of pigments using salts of alkyl esters of olefin-maleic anhydride copolymers |
NL6507437A (en) * | 1964-08-12 | 1966-02-14 | ||
US3261798A (en) * | 1964-11-12 | 1966-07-19 | Monsanto Co | Paper treating solution of an alphaolefin/maleic anhydride copolymer and a bisulfite |
US3706704A (en) * | 1966-10-25 | 1972-12-19 | Gulf Research Development Co | Preparation of c6-c10 olefin-maleic anhydride copolymers |
US3598778A (en) * | 1967-01-19 | 1971-08-10 | Gulf Research Development Co | Ammonium hydroxide polymer solutions for floor polish compositions |
DE1621693B2 (en) * | 1968-02-23 | 1975-06-19 | Bayer Ag, 5090 Leverkusen | Anionic paper sizing agents |
-
1973
- 1973-12-11 DE DE2361544A patent/DE2361544C3/en not_active Expired
-
1974
- 1974-11-27 NO NO744281A patent/NO141056B/en unknown
- 1974-12-05 US US05/529,695 patent/US4152312A/en not_active Expired - Lifetime
- 1974-12-09 BE BE151304A patent/BE823120A/en unknown
- 1974-12-09 NL NL7416003A patent/NL7416003A/en not_active Application Discontinuation
- 1974-12-09 CA CA215,542A patent/CA1030287A/en not_active Expired
- 1974-12-09 AT AT980774A patent/AT340767B/en not_active IP Right Cessation
- 1974-12-09 IT IT54423/74A patent/IT1024366B/en active
- 1974-12-09 FI FI3538/74A patent/FI353874A/fi unknown
- 1974-12-10 ES ES432768A patent/ES432768A1/en not_active Expired
- 1974-12-10 JP JP49141220A patent/JPS5926719B2/en not_active Expired
- 1974-12-10 SE SE7415467A patent/SE419109B/en unknown
- 1974-12-11 GB GB53565/74A patent/GB1483929A/en not_active Expired
- 1974-12-11 CH CH1650274A patent/CH600038A5/xx not_active IP Right Cessation
- 1974-12-11 FR FR7440806A patent/FR2253871B1/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CH600038A5 (en) | 1978-06-15 |
FR2253871B1 (en) | 1978-09-15 |
FI353874A (en) | 1975-06-12 |
GB1483929A (en) | 1977-08-24 |
JPS5926719B2 (en) | 1984-06-29 |
DE2361544C3 (en) | 1982-07-29 |
IT1024366B (en) | 1978-06-20 |
FR2253871A1 (en) | 1975-07-04 |
ES432768A1 (en) | 1977-01-01 |
BE823120A (en) | 1975-06-09 |
NO744281L (en) | 1975-07-07 |
ATA980774A (en) | 1977-04-15 |
DE2361544B2 (en) | 1977-01-27 |
US4152312A (en) | 1979-05-01 |
CA1030287A (en) | 1978-04-25 |
SE419109B (en) | 1981-07-13 |
NL7416003A (en) | 1975-06-13 |
JPS5089603A (en) | 1975-07-18 |
SE7415467L (en) | 1975-06-12 |
AT340767B (en) | 1978-01-10 |
DE2361544A1 (en) | 1975-06-19 |
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